https://doi.org/10.15415/jnp.2017.

51003

X-Ray Fluorescence Analysis of Ground Coffee

MARÍA CRISTINA HERNÁNDEZ1, DARÍO ROMERO1, HUMBERTO TORRES1,
JAVIER MIRANDA2,3*, AND A. ENRIQUE HERNÁNDEZ-LÓPEZ2

1
Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior,
04510, Coyoacán, Cd. Mx., MEXICO
2
I nstituto de Física, Universidad Nacional Autónoma de México, Apartado Postal 20-
364, 01000 Álvaro Obregón, Cd. Mx., MEXICO
3
C
 entro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México,
Circuito Investigación Científica, 04510, Coyoacán, Cd. Mx., MEXICO

*Email: miranda@fisica.unam.mx
Published online: August 07, 2017
The Author(s) 2017. This article is published with open access at www.chitkara.edu.
in/publications

Abstract  Coffee is becoming one of the most popular beverages in Mexico.

In the present work, X-ray Fluorescence (XRF) was used to determine the
contents of several elements (with atomic numbers between 11 and 38) in 11
samples of commercial ground coffee, comparing with another one of soluble
coffee and two of used ground coffee. Samples were dried at room temperature
and pelletized. XRF analyses were carried out using a spectrometer based on
an Rh X-ray tube, registering the characteristic x-rays with a Silicon Drift
Detector. The system detection calibration and accuracy check was performed
through the analysis of NIST certified reference materials 1547 (peach leaves),
1570a (spinach leaves), 1573a (tomato leaves), and 1571 (orchid leaves). As a
general rule, the elemental concentrations measured are similar in all samples
of coffee, in values not exceeding toxic levels. However, the differences
among the elemental concentrations are shown.
Keywords: Ground coffee, Elemental analysis, XRF, Food analysis.

1. INTRODUCTION
Coffee is nowadays among the most popular beverages in Mexico. There was
Journal of Nuclear
an estimated production in the country of 1 × 106 ton during the cycle 2014- Physics, Material
2015, in 7.3 × 105 hectares of land. Moreover, coffee consumption grew at a Sciences, Radiation and
rate of around 5% per year until 2015, reaching a total of 1.1 × 106 ton [1]. Applications
Vol-5 No-1
August 2017
pp. 25–34

25
Hernández, M.C. Of this, 78% corresponds to instant coffee and the remaining 22% to ground
Romero, D. coffee.
Torres, H. Coffee is grown as two species: Cofea arabica and Cofea canephora.
Miranda, J. They are commonly known as arabica and robusta. Its active substance is
Hernández-López, the alkaloid caffeine. Effects of coffee on human health are still under strong
A.E.
debate. Some authors suggest that drinking two to four cups of coffee per day
benefit health, reducing the risk of colon cancer, gallstones, liver cirrhosis and
Parkinson’s disease [2, 3].
Processing starts from green coffee beans subjected to a thermal procedure,
ending as roasted coffee beans. To produce instant coffee, the soluble and
volatile components of the roasted beans are extracted. They provide the
coffee aroma and flavor; it is possible to do it by means of water. Pressurized
liquid water heated to around 175 °C is employed for this process. The coffee
concentration in the resulting liquid is then augmented by either evaporation
or freeze concentration.
Due to the economical relevance of coffee, extensive research has
been published, in particular regarding its elemental composition, using
many analytical techniques. For instance, Atomic Absorption Spectroscopy
(AAS) was used by Grembecka et al. [3] to determine concentrations of 14
elements, and used them to differentiate the types of coffee (ground, instant)
using multivariate statistics. Valentin and Watling [4] employed Inductively
Coupled Plasma spectroscopies (ICP) to determine the provenance of coffee
samples from 15 countries, based on the contents of 59 elements. Antoine
et al. [5], with measurements through Neutron Activation Analysis (NAA)
and other methods, determined the origin of ground coffee consumed in
Jamaica. Debastiani et al. [6] analyzed Brazilian coffee samples with Particle
Induced X-ray Emission (PIXE). Finally, Martín et al. [7] were able to
establish differences between arabica and robusta samples based on elemental
concentrations measured with ICP.
Furthermore, several studies have been conducted recently to determine
the elemental concentrations in several types of food with high consumption in
Mexico, employing x-ray spectrometric methods, such as X-ray Fluorescence
(XRF) or PIXE. This way, elemental contents in tomato paste samples from
five countries were determined using PIXE and ion backscattering [8].
Also, concentrations in many varieties of dried chili peppers were measured
with XRF, finding unusually elevated values for Br [9]. Additionally, the
concentrations of 10 elements were determined in commercial breakfast
cereals of several types using XRF and PIXE [10].
With all this in mind, it was considered important to start a more thorough
characterization of coffee consumed in Mexico, both ground and instant, either

26
to determine its nutritional properties, purity, or origin. As a first step, this X-Ray
work is aimed to demonstrate the viability of using XRF to quantify elemental Fluorescence
concentrations in ground coffee samples, both fresh and used, as well as Analysis of Ground
instant coffee. The data should provide information about possible differences Coffee
in several elements, which might be fixed as indicators of coffee properties or
provenance.

2. MATERIALS AND METHODS

Three types of coffee samples were obtained: ground coffee (11 samples),
used ground coffee (two samples), and instant coffee (one sample). All of them
were dried at room temperature, ground in an agate mortar and deposited inside
polyethylene vials covered with 3.5 µm thick Mylar® films. A description of
the samples is presented in Table 1. In general, it was not possible to determine
if the samples were arabica or robusta.
XRF analysis was carried out using a spectrometer based on an Rh anode
x-ray tube [11], with x-ray spectra detection through an Amptek® X-123SDD
complete spectrometer (Bedford, MA, USA). The tube operated at a 35 kV
voltage and a 500 µA current. Under these working conditions, primary photon
scattering in the samples was strongly reduced. Collection time for each
spectrum was 600 s. The spectra were collected with the attached Amptek®
multichannel buffer and a personal computer. Pressure at the irradiation
chamber was of the order of 5 × 10­­–6 torr.

Table 1: Description of coffee samples.

Sample Type
Jekemir Ground
Member´s Mark Ground
Los Portales Ground
Member´s Mark (arabiga) Ground
Chiapaneco Ground
La Onza (Coatepec) Ground
Capeltic (Chiapas) Ground
Blasón Gourmet Ground
Casero 1 (arabiga) Ground
Casero 2 (arabiga) Ground
Cafesín Ground and used
Diemme Ground and used
Dolce Gosto (Lungo) Ground (capsule)
Nescafé Dolca Instant

27
Hernández, M.C. The system detection calibration was performed through the analysis of
Romero, D. National Institute of Standards and Technology (NIST) certified reference
Torres, H. materials 1547 (peach leaves), 1570a (spinach leaves), and 1573a (tomato
Miranda, J. leaves). Accuracy determination was then done by analyzing a sample of NIST
Hernández-López, reference material 1571 (orchard leaves). Spectra were deconvoluted with the
A.E.
open-access QXAS computer code [12].

3. RESULTS AND DISCUSSION

The first result is the accuracy determination after analysis of the orchard
leaves standard (NIST 1571). The elements P, S, Cl, K, Ca, Mn, Fe, Cu, Zn,
Br, Rb, and Sr were detected, quantified, and compared to the values given
in the certificate. All of the measured elemental concentrations, except S
and Cl, agree with the certified values within 20% or are even equal. In
the case of S and Cl the disagreement (60% and –24%, respectively) is
explained because their concentrations are not certified in the reference
material. The overall consequence is that XRF may be considered as
reliable in this study.
Regarding the coffee samples, a total of 14 elements were found: Na, Mg,
P, S, K, Ca, Cr, Mn, Fe, Cu, Zn, Br, Rb, and Sr. Table 2 displays the average
elemental concentrations in ground coffee, as well as the data for used ground
coffee and instant coffee, all for dry mass. Experimental uncertainties range
from 15% for trace elements (like Na, Mn, Cu, Zn, Sr), down to 4% for the
major elements (K, Ca).
The concentrations of nine elements (Na, Mg, S, Mn, Fe, Cu, Zn, Rb,
Sr) were similar among all the samples, including the used and instant
coffee. An exception is Fe for the Los Portales sample, with a 560 mg
kg-1 value, which is extremely high and may be attributed to the grinding
machine used to process the roasted coffee. Nevertheless, the remaining
elements showed strong differences among new ground coffee, used coffee,
and instant coffee. Figure 1 presents the major nutrients Na, P, K, and Ca
data for all samples, while Figure 2 displays concentrations of Cr and Br.
In the case of Na, it is readily seen that no pattern can be identified for the
three kinds of samples, as stated above. However, P, K, and Ca are strongly
reduced in the used samples, most probably by a scavenging process by
hot water during the brewing process. Additionally, Cr is increased in the
Cafesín sample, possibly because a contamination from the coffee maker.
Finally, the instant coffee sample Dolca has very high contents of Br. This
is not easily explained, unless the manufacturer employs some Br-based
compound as pesticide.

28
 X-Ray
Fluorescence
Analysis of Ground
Coffee

29
Hernández, M.C.
Romero, D.
Torres, H.
Miranda, J.
Hernández-López,
A.E.

Figure 1: Concentrations of major nutrients Na, P, K, and Ca determined in coffee

samples.

30
 X-Ray
Fluorescence
Analysis of Ground
Coffee

Figure 2: Concentrations of elements Cr and Br determined in coffee samples.

31
Hernández, M.C. Table 2: Elemental concentrations determined in coffee samples: mean, minimum, and
Romero, D. maximum for ground, coffee; used (Cafesín and Diemme), and instant coffee Dolca.
Torres, H.
Miranda, J. Element Units Mean Minimum Maximum Used Used Dolca
Hernández-López, ground ground ground Cafesín Diemme
A.E. coffee coffee coffee
Na mg kg–1 29 9.2 47 44 20 42
Mg % 0.20 0 0.38 0 0.11 0.24
P % 0.22 0.17 0.36 0.81 0.81 0.21
S % 0.18 0.15 0.21 0.067 0.079 0.096
K % 4.3 3.4 7.5 0.55 0.46 4.7
Ca % 0.35 0.26 0.43 0.22 0.23 0.20
Cr mg kg–1 2.1 0.74 4.6 6.2 2.9 1.7
Mn mg kg –1
47 18 82 13 26 14
Fe mg kg –1
143 85 560 75 69 72
Cu mg kg –1
5.8 2.1 7.6 6.7 9.9 1.2
Zn mg kg –1
9.7 2.1 20 11 20 5.2
Br mg kg –1
15 11 21 4.7 12 32
Rb mg kg –1
18 10 25 2.5 9.9 18
Sr mg kg–1 35 17 49 8.3 18 9.2

A further test in the analytical results can be carried out through a

comparison with other published works where results of elemental analyses of
ground coffee samples were presented. Table 3 displays such data for selected
elements, compared to the average of ground coffee from this work. It is
possible to see that concentrations in the latter values are of the same order as
those of the previous papers, although higher for K, Ca, and Fe. More research
must be followed to find out the explanation of the higher averages.

Table 3: Comparison of elemental concentrations in ground coffee published in

several studies.

Source P K Ca Mn Fe Cu Zn
% % % mg mg mg mg
kg–1 kg–1 kg–1 kg–1
Martín et al. [7] 0.12 1.27 0.088 28 40 11.9 5.1
Antoine et al. [5] 0.14 1.88 0.13 23 39 12.6 6.3

32
 Ranic et al. [13] – 1.81 0.11 33 39 18 6.0 X-Ray
Fluorescence
Grembecka et 0.23 1.37 0.084 22 42 16.1 5.3 Analysis of Ground
al. [3] Coffee
Debastiani et 0.27 2.13 0.14 33 65 19.4 8.4
al. [6]
Anderson [14] 0.20 1.90 0.12 25 13 14.0 8.0
This work 0.22 4.30 0.35 47 143 5.8 9.7

As discussed in all the works cited in Table 3, the concentrations measured

for every element are not expected to reach toxic levels. Regrettably, no
official standards exist for elemental concentrations in ground coffee, not even
in the Codex Alimentarius, the official standard for many foods developed by
the Food and Agriculture Organization. Thus, it is not possible to state if the
measured concentrations fulfill any official limit in ground coffee.

CONCLUSIONS
From the results presented above, it is possible to assure that the analyses
with XRF are accurate. Moreover, there are significant differences in the
concentrations of several elements (like P, K, Ca) among roasted ground
coffee, used ground coffee, and instant coffee specimens, probably because
water drags these elements during the brewing. Instant coffee has very high Br
concentration and used coffee may present Cr contamination during brewing.
Elemental contents are similar to those determined in previous studies of
roasted ground coffee, although the average looks higher for a few cases. It
is not possible to see a definite disagreement in elemental concentrations to
identify origin of the samples.
For future work, an extensive collection of samples must be carried out,
including more instant coffee samples. The origin of coffee samples must be
clearly established, possibly with the application of multivariate statistical
analysis (like Principal Component Analysis) to a wider sample set. Finally,
samples obtained directly from producers might be collected.

ACKNOWLEDGEMENTS
The authors acknowledge the technical assistance of J.C. Pineda. Work
supported in part by DGAPA-UNAM (PAPIME PE104814 and PAPIIT
IN102615).

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